ORIGIN AND ESTIMATION OF THE GUSHING POTENTIAL OF ISOMERIZED HOP EXTRACTS

Two types of gushing promoter have been isolated from isomerized hop extracts. One type is a humulinicacid dehydration product which occurs rarely insuch extracts. The other type of gushing promoter consists of a mixture of oxidation products of hop resins, and is present in all the isomerized extracts examined. The higher the concentration of these oxidation products in a beer the greater is its tendency to gush. α-Acids and cohulupone have been shown to be effective gushing inhibitors. The gushing potential of an isomerized extract appears to be determined mainly by the relative proportions of oxidized materials and unchanged α-acid, present as contaminants. A method for determining the gushing susceptibility of a beer is described.     

THE EFFECT OF HOP SUBSTANCES ON THE PRODUCTION OF FUSEL OIL

Unhopped beers contain more fusel oils than the corresponding normally hopped beers when certain strains of yeasts are used during fermentation. Water soluble fractions of hops and some soft resin constituents can influence fusel oil production. When hops are completely replaced by isomerized hop extracts the use of some additional hop fraction in the copper leads to the resulting beer having a similar fusel oil content to one hopped in the usual way. Partially hopped beers (0·25 lb./brl.) usually have similar fusel oil contents to beers produced using the normal quantity of hops (1·0 lb./brl.).     

INSTITUTE OF BREWING: ANALYSIS COMMITTEE THE DETERMINATION OF HOP OIL

A distillation method using a modified version of the Connery and Wright technique or a B.P. still and measurement of the oil fraction by volume is recommended for the determination of the essential oil content of hops and hop powders.     

Impact of Different Hop Compounds on the Overfoaming Volume of Beer Caused by Primary Gushing

When weather conditions favour the growth of moulds on barley, beers brewed from the resulting malts often tend to gush. Certain Fusarium species (e.g., F. graminearum and F. culmorum) may cause this problem. Supersaturated with CO₂, a primary gushing beer contains an overcritical concentration of microbubbles; these are reputed to be stabilised by Fusarium‐derived hydrophobins. Research with varying brewhouse parameters has been performed to investigate the factors of primary gushing. As hops are known to contribute to a wide range of both gushing positive and negative substances in beer, the hopping regime has emerged as an important aspect. This paper examines the impact of different hop varieties on gushing. Hop oils and unsaturated fatty acids are reputed to be gushing‐suppressors. Compounds such as dehydrated humulinic acid can intensify the effect. Hop pellets, with a prevalent range of conductometric values (5–10% α‐acid), commonly employed in breweries to adjust bitterness and aroma were selected. By working with the same “gushing malt”, the spectrum of compounds in the finished beer only differed through the hop product used. The overfoaming volumes of different samples were determined according to MEBAK guidelines. Respective hop oil and fatty acid concentrations (by GC) and iso‐α‐acid contents (by HPLC) were compared and a chronological sequence of the changing percentages of beer loss is shown.     

AUTOMATED REPORTING ON THE QUALITY OF HOPS AND HOP PRODUCTS

The quality of a hop variety or a hop product can readily be assessed by a fully automated sequence of selective extraction, fractionation and quantitative analysis. To illustrate the elegance of the method, nine hop varieties and three hop extracts were compared with respect to the content of important marker compounds in the hop oils and of the hop acids. Supercritical fluid extraction at different densities of carbon dioxide was applied to extract selectively, the hop oils and the hop acids, respectively. The hop oils were further fractionated into an apolar and a polar fraction by solid phase extraction and consecutive elution with n-hexane and ethyl acetate. Separation and identification were achieved by capillary gas chromatography coupled to mass spectrometry. Myrcene, β;-caryophyllene, α;-humulene and β;-farnesene in the apolar fraction, linalool, undecan-2-one, tridecan-2-one and humuladienone in the polar fraction were selected for quantitative evaluation of the respective hop oils. Sulphur-containing compounds were revealed by capillary gas chromatography using sulphur-selective atomic emission detection. Complete separation and quantification of all hop α;-acids and β;-acids was effected by microemulsion electrokinetic chromatography coupled to diode array detection .     

THE ESSENTIAL OIL OF HOPS A REVIEW

The composition of essential oil of hops is reviewed and the nature of hop oil components which survive into wort and beer is discussed. Methods which are available to the brewer for imparting hop character to beer are critically evaluated.     

Induction of Gushing with Recombinant Class II Hydrophobin FcHyd5p from Fusarium culmorum and the Impact of Hop Compounds on its Gushing Potential

Malt‐induced gushing is a problem that has been known for many years. Mechanisms and inducing agents are still not fully understood and identified. Hydrophobins produced by various filamentous fungi are currently under discussion as biological gushing‐inducing compounds. In the current study the class II hydrophobin FcHyd5p, from the cereal pathogen Fusarium culmorum, was employed in beer and other carbonated beverages for gushing experiments and the influence of hop compounds on gushing potential was examined. It was demonstrated that this protein strongly induces gushing in various carbonated beverages, including beer. It was further demonstrated that the resulting gushing volume is susceptible to certain hop compounds and can be decreased significantly by the addition of these substances.     

TRACE VOLATILE CONSTITUENTS OF BEER. HOP SEED OIL

The fatty acid profile of hop seed oil has been examined and shown to be very similar to the fatty acid profile of the lipid fraction of both hops from which the seeds have been removed and seedless hops. The fates of the hop lipids and in particular the fatty acid fraction, both in conventional hopping procedures and in the preparation of an isomerised extract are discussed with reference to their possible effect on beer flavour.     

DIFFERENCES IN UTILISATION OF THE ESSENTIAL OIL OF HOPS DURING THE PRODUCTION OF DRY-HOPPED AND LATE-HOPPED BEERS

Late-hopped and dry-hopped beers were prepared and their lipophilic constituents extracted using Amberlite XAD-2 resin. Examination of the volatile constituents by GC-MS confirmed that most of the hop oil added towards the end of wort boiling is lost by evaporation. Part of the material which survives boiling is chemically transformed by yeast during fermentation. Dry-hopped beer contained compounds more representative of the original hop oil than did the corresponding late-hopped beer. A liquid carbon dioxide extract of hops, rich in essential oil, has been fractionated by column chromatography on alumina-silica giving preparations which simulate either late-hop or dry-hop character.     

THE MANUFACTURE OF HOP CONCENTRATES AND EXTRACTS*

Manufacture of the traditional hop concentrate (i.e., a product containing the chemically unchanged natural hop constituents apart from useless inert material) is increasing both in Europe and in America; this traditional concentrate, which is added to the copper, retains the varietal characteristics of the parent hop. In determining replacement ratios it is important to assess bitterness by tasting trials, as analytical assessments of bitterness may give misleadingly low results when concentrates are used. Although chemically pre-isomerized extracts can be prepared for addition to sweet beer, it is improbable that this type of extract will be used extensively until a great deal more is known about transformations which take place during hop boiling; such an extract, however, does allow maximum utilization of hop bittering principles. The selection of hops for high α acid content and the separate addition of the flavour components such as hop oil appears to be a desirable development for the near future.     

STABILITY OF ESSENTIAL OIL OF HOPS

The stability of hop essential oil in beers, in hops and in aqueous emulsions has been investigated. Hop character of beers treated with hop oil emulsion has stability on pasteurization and storage similar to that of dry hopped beers. When bottled with high levels of headspace air, beers lose hop character. Beers dry-hopped with stored hops or with hops damaged during pelleting tend to develop sulphury flavours. However, hop oil emulsions prepared from such hops give rise to a sound hop character in beer. Hop oil emulsion produced by the new process shows good stability physically, chemically and biologically, particularly when mechanically homogenized and stored under an inert atmosphere. The extent of any chemical alteration due to contact with air may be estimated spectrophotometrically.     

THE AROMA OF HOPS. II. ON THE COMPOSITION OF HOP OIL

Hop oil was investigated by gas chromatography coupled to a mass spectrometer. Almost all substances were obtained by preparative gas chromatography in amounts sufficient for N.M.R. spectral identification. Hop oil was separated into hydrocarbon- acid- alcohol- and ketone-containing fractions using adsorption chromatography, saponification, alkaline extraction and extraction with Girard T reagent. Fifty-three substances were identified of which sixteen have not been recorded previously as occurring in hop oil.     

The Oxygenated Sesquiterpenoid Fraction of Hops in Relation to the Spicy Hop Character of Beer

Hop‐derived sesquiterpenoid‐type oxidation products have been associated with a spicy or herbal hoppy beer character. However, the flavour threshold values of hitherto identified oxygenated sesquiterpenes are generally much higher than their estimated levels in beer. By applying two‐step supercritical fluid extraction of hop pellets using carbon dioxide, followed by chromatographic purification of the enriched sesquiterpenoid fraction, highly specific varietal hop oil essences containing all main oxygenated sesquiterpenes were obtained. Post‐fermentation addition (at ppb levels) of these purified sesquiterpenoid essences from various European aroma hops led to distinctive spicy or herbal flavour notes, reminiscent of typical ‘noble’ hop aroma. It is concluded that a spicy hop flavour impression in beer depends significantly on minor constituents of the natural sesquiterpenoid hop oil fraction.     

PREPARATION OF OIL RICH HOP EXTRACTS AND THEIR ADDITION TO BEER ON THE PILOT-SCALE USING LIQUID CARBON DIOXIDE*

The introduction of carbon dioxide hop extracts dissolved in liquid carbon dioxide to green beer during transfer from fermentation vessel to cold conditioning tank results in a sound dry hop flavour in the finished product. A system has been developed for injecting a solution of extract into a beer main. Extracts which are rich in hop oils are particularly suitable for imparting hop character to beer and a liquid-liquid countercurrent procedure is described for producing extract fractions containing enhanced levels of essential oil.     

EFFECT OF OIL CONTENT ON THE LOSS OF ALPHA-ACID FROM HOPS DURING STORAGE

Examination of a wide range of hop varieties showed that the percentage loss of α-acid in storage was related to the essential oil content of the samples. Seedless hops, having higher oil contents, lost more α-acid than seeded hops of the same variety. The variety Bullion grown for isomerized extract manufacture should be picked 7–10 days earlier than normal to minimize loss of α-acid before processing.     

STABILITY OF AQUEOUS EMULSIONS OF THE ESSENTIAL OIL OF HOPS

Hop oil emulsions prepared from different varieties of hops have been found to exhibit enhanced physical stability on the addition of blends of the emulsifiers Span 20/Tween 80 or Span 60/Tween 60. Examination of the particle size and volume distributions of an emulsion by use of a Coulter Counter was found to be an excellent method of monitoring its stability. An indication as to the relative efficiency of emulsifiers can be obtained from Coulter Counter measurements on hop oil emulsions after storage for 4 days. The use of an ultracentrifuge provies a rapid means of testing emulsion stability and hence the effectiveness of emulsion stabilizers.     

THE STORAGE OF PELLETED POWDERS MADE FROM WYE NORTHDOWN HOPS

Pelleted hop powder from seeded Wye Northdown hops of the 1976 crop shows small losses in lead conductance value (LCV) when stored in commercial packs for ca. 12 months after processing. The losses for hop pellets stored at ambient temperature are slightly more rapid than for those stored at 0 to 4°C. Losses in LCV of pellets during storage in the cold or at ambient temperature are substantially less than those of seeded Wye Northdown cone hops stored in pockets under comparable conditions. The hop pellets showed no significant loss in oil content or bittering potential over the storage period. Taste panels were unable to detect differences in flavour when comparisons were made of beers bittered with pellets stored in the cold and at ambient temperature.     

HOP PRODUCTS

Hop products have established an important and permanent position in the brewing raw materials market. Hop pellets and hop extract offer significant advantages to traditional brewers. However, the ultimate hop product is the isomerised hop extract, which can now be produced without the involvement of organic solvents. Still to be resolved and hence controlled is the contribution of the hop oil fraction to beer flavour.     

THE AROMA OF HOPS I. ORIGIN AND IDENTIFICATION OF HOP AROMA SUBSTANCES

Gas chromatography of the head space was used to follow the evolution of hop aroma under different conditions of storage. Aroma from fresh hops contains mainly myrcene, which disappears as the hops get older. Meanwhile new, more volatile substances are formed, especially by degradation of the well-known α- and β-acids; when hops are kept in closed storage the aroma therefore soon takes a composite character. When the formed volatiles are allowed to escape, the aroma of hops becomes poorer with age, to disappear almost completely in the end. Twenty-five compounds have been identified in the more volatile fraction of hop extracts.     

FATTY ACIDS IN ISOMERIZED HOP EXTRACTS AND GUSHING

A procedure is described for the analysis of fatty acids (C₁₂-C₁₈ individually and C₁₈₊ as a group) in hops, hop extracts and isomerized hop extracts, and analytical results are quoted for twenty-one different samples of hops or hop products. Isomerized extracts varied widely in their content of fatty acids and isomerization and processing of hops appeared to eliminate some fatty acids selectively so that isomerized extracts were enriched in palmitic acid, linoleic acid and linolenic acid. Some hop extracts had a surprisingly high content of lauric acid. The analytical results are discussed in relation to gushing.